DE615707C - Process for the preparation of 1-alkylamino-4-arylaminoanthraquinones - Google Patents

Description

ι - alkylamino - 4 - arylaminoanthraquinones are known to be valuable intermediates for the production of dyes Anthraquinone series. A number of such products are also used to color cellulose esters and ethers, especially acetate silk, are used.

The i-alkylamino-4-arylaminoanthraquinones have been prepared so far that the two substituted into the anthraquinone molecule in separate operations Amino groups were introduced. It has now been found that the introduction of the two substituted Afnino residues into the anthraquinone molecule in one operation can combine, if one on i, 4-Dioxyanthraquinones in the presence or in the form of their leuco bodies or in the presence of suitable ones An arylamine and a reducing agent

so alkylamine can act simultaneously or in succession, where appropriate the Reaction is carried out with the addition of condensing agents. Under the i, 4 - Dioxyanthraquinones can be named: Quinizarin, also products such as i, 4, 5 - trioxyanthraquinone or 1, 4, 5, 8-tetraoxyanthraquinone. Among the arylamines there may be aniline, p-toluidine, but in particular p-aminophenol and p-phenylenediamine may be mentioned. Among the alkyl amines can Methylamine, ethyl amine, oxyethylamine, oxypropylamine, etc. are mentioned, with also the oxyalkyiamines are particularly suitable for smoothly carrying out the reaction. the obtained condensation products consist of anthraquinone derivatives, depending on the Amount of the reducing agent or leucoanthraquinone derivatives originally present contain more or less leuco compounds. It is therefore advisable to subject the condensation products to an oxidation process to subject so that they are completely converted into real anthraquinone derivatives will. The products obtained in this way can optionally be subjected to a cleaning process be subjected to e.g. B. by dissolving from suitable solvents. If one has condensation products, whose basicity is such that they are soluble in dilute mineral acids, they are best obtained through Dissolving purified from a dilute acid.

Can be used to manufacture products intended for dyeing acetate silk it may be useful in certain cases instead of a specific arylamine and a certain alkylamine to use mixtures that consist of two or more Aryl amines or two or more alkyl amines exist. The resulting

Mixtures are characterized by a noticeably increased affinity compared to the pure products to the acetate silk.

Example ι

9 parts of leucoquinizarine and 9 parts of quinizarine are mixed with 90 parts of ethyl alcohol 6 parts /? - oxyethylamine and 10.5 parts

p-phenylenediamine heated to boiling for 24 hours. It is filtered cold and washed with ethyl alcohol and water, heated the filter residue with 400 parts of 7% hydrochloric acid, filtered and washed with hot water. The formed i - /? - oxyäthylamino-4- (4'-amino) -phenylaminoanthraquinone is in the filtrate and can be neutralized be precipitated in the cold with milk of lime or soda. By pouring on ice and alkali and grinding with suitable With additives, the dye is brought into a form suitable for dyeing acetate silk. It dyes acetate silk in pure green shades with good fastness properties.

Example 2

12 parts of leucoquinizarin be with 6 parts of p-phenylenediamine, 6,8 parts of a 24 ° / ^s oig solution of methylamine in ethyl alcohol, 1.4 parts of sodium chlorate and 4 parts of dried boric acid in 80 parts of ethyl alcohol in · an enamelled autoclave about 20 Heated to 90 ⁰ hours. It is filtered cold, washed with ethyl alcohol and water and i-methylamino-4-p-phenylenediaminoanthraquinone is obtained in good yield. The product dissolves in ethyl acetate with blue-green and in conc. Sulfuric acid with a purple-blue color. The reaction proceeds similarly with p-aminophenol, p-tolylenediamine etc. instead of p-phenylenediamine and ethylamine, propylamine etc. instead of methylamine.

Example 3

9 parts of leucoquinizarin and quinizarin are 9 parts in 90 parts of ethyl alcohol with 4 parts /? - Oxyäthylamin, 3 parts of 27 ° / _o ethyl methyl amine and 10 parts of p-phenylenediamine is heated to boiling for about 24 hours. The product is worked up in a manner similar to that given in Example 1, and a dye is obtained which, after suitable pasting, dyes acetate silk in very strong green tones.

Example 4

240 parts leucoquinizarin together with 1000 parts of methyl alcohol and 110 parts of p-phenylenediamine several hours in a closed apparatus at 90 ⁰ heated. 85 parts of 5-oxyethylamine, 35 parts of sodium chlorate and 80 parts of dried boric acid are then added and the mixture is then heated under the reflux condenser until the originally yellow-brown liquid has first turned green and then blue and the color no longer changes. After cooling, it is filtered, washed with methyl alcohol and dried.

Example 5

6 parts of leucoquinizarin are used as a fine paste in a total of 30 parts of water 1.8 parts /? - oxyethylamine and 3 parts Heat p-phenylenediamine on a boiling water bath for about 15 hours. The received Leuco product is oxidized in the usual way and then purified analogously to Example 1.

Example 6

60 parts of leucoquinizarin in 200 parts of aniline with 16.5 parts of 5-oxyethylamine are heated to 45 to 60 ° for 6 hours. Now is added 8 parts of sodium chlorate and 20 parts of boric acid are added and heated for several hours at 65 to 70 ^0, wherein the first resultant 90 'leuco-i-oxy-4 - ^ - oxyäthylaminoanthrachinon in i ~ phenylamino-4 / S-oxyäthylaminoanthrachinon converted is what one z. B. fails with benzene. After suitable pasting, the body colors acetate silk in strong blue tones.

Example 7

60 parts of leucoquinizarin are in 300 parts of methyl alcohol with 16.5 parts /? - oxyethylamine heated to 45 to 60 ° for about 6 hours. 30 parts of p-toluidine and 8 parts are added Sodium chlorate and 20 parts of boric acid are added and the mixture is heated to 70 to 80 ° for several hours. The resulting i-p-tolylamino-4-yS-oxyethylaminoanthraquinone is, after the methyl alcohol has been distilled off, precipitated with benzene. The sulfonated product dyes wool in pure blue tones.

Instead of p-tohiidine one can also use m-toluidine, Use p-anisidine, p-aminophenol, etc. The dyes obtainable in this way dye acetate silk in blue to blue-green tones, and after sulfonation they dye wool from acid baths in similar tones.

Example 8

60 parts of leucoquinizarin are heated in 300 parts of methyl alcohol with 35 parts of a 19 ^Q / _O solution of methylamine in methyl alcohol for several hours at 60 to 70 °. 60 parts of aniline and 20 parts are added

Boric acid and 8 parts of sodium chlorate added and heated for several hours at 65 to 90 ^0th The dye obtained dyes acetate silk in strong blue tones after suitable pasting.

Example 9

100 parts of leukochinizarin are heated to 90 ° for several hours in 100 parts of methyl alcohol with 55 parts of p-phenylenediamine. Then one adds 32.5 parts / 5-Oxyäthylamin, 27 parts of a I9 ° / _O by weight solution of methylamine in methyl alcohol, 17.5 parts of sodium chlorate and 40 parts of boric acid, and heated for several hours to 65 ^0th After cooling, the precipitated condensation product is filtered off.

The resulting dye stains acetate silk in strong colors after suitable pasting green tones.

Claims (1)

Claim: Process for the preparation of i-alkylamino-4-arylaminoanthraquinones, characterized in that 1, 4-D1-oxyanthraquinones in the presence or in the form of their leuco derivatives or in the presence of reducing agents, with or without the addition of condensing agents, aliphatic and aromatic amines, in particular p-phenylenediamine and p-aminophenol act in one operation leaves.